CN1656053A - Process for the production of acetic acid - Google Patents
Process for the production of acetic acid Download PDFInfo
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- CN1656053A CN1656053A CNA038116243A CN03811624A CN1656053A CN 1656053 A CN1656053 A CN 1656053A CN A038116243 A CNA038116243 A CN A038116243A CN 03811624 A CN03811624 A CN 03811624A CN 1656053 A CN1656053 A CN 1656053A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/08—Acetic acid
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Abstract
A process for the production of acetic acid which comprises carbonylating methanol and/or a reactive derivative thereof in one or more reactors in a liquid reaction composition comprising iridium carbonylation catalyst, ruthenium promoter, methyl iodide co-catalyst, methyl acetate, acetic acid and water. The liquid reaction composition from the one or more reactors is passed to one or more flash separation stages to form (i) a vapour fraction comprising condensable components and a low pressure off-gas comprising carbon monoxide and (ii) a liquid fraction comprising iridium carbonylation catalyst, ruthenium promoter and acetic acid solvent. The condensable components are separated from the low pressure off-gas. The concentration of carbon monoxide in the low pressure off-gas is maintained according to the formula: Y>mX+C wherein Y is the molar concentration of carbon monoxide in the low pressure off-gas, X is the concentration in ppm by weight of ruthenium in the liquid reaction composition, m is about 0.012 and C is about -8.7.
Description
The present invention relates to a kind of carbonylation of methanol and produce the method for acetate, relate in particular to the method that iridium carbonylating catalyst and ruthenium promotor exist carbonylation of methanol down to produce acetate.
The method that iridium catalyst and ruthenium promotor exist carbonylation of methanol down to produce acetate, for example, be described among US5672743, EP-A-0752406, EP-A-0849248, EP-A-0849249, EP-A-0849250, EP-A-0999198 and the EP-A-1002785.In this liquid-phase carbonylation method, can reclaim acetic acid product by the following method: take out the liquid-phase carbonylation composition in by carbonylation reactor, make composition experience one or more separation phases, send other component of composition back to carbonylation reactor again with acetic acid product.
Several pieces of patent applications all are the stability problems about iridium carbonylating catalyst in the product removal process, for example, and WO96/14286 and EP-A-0616997.
US5,237,097 relate to a kind of carbonylation method, wherein liquid-phase carbonylation product solution are delivered to the disengaging zone, and this disengaging zone stagnation pressure is lower than reaction zone pressure, simultaneously, introduces the gas contain carbon monoxide so that the dividing potential drop of the highest 30psia to be provided to the disengaging zone stagnation pressure.The preferred rhodium of catalyzer, ruthenium, palladium, cobalt and the nickel that contain the group VIII metal, wherein preferred especially rhodium, cobalt and nickel, but only rhodium is illustrated, and be the theme of claim.
EP-A-0728729 relates to the purification process that liquid-phase carbonylation reacts the carboxylic acid that makes, wherein do not exist carbon monoxide or carbon monoxide pressure of tension to depress less than the branch in the carbonylation reactor, volatile iridium and/or volatile catalytic promoter (for example ruthenium, osmium and rhenium) impurity that helps altogether contact the non-volatile form that is converted into iodide.State that wherein carbon monoxide pressure of tension can be the 0-5 crust, preferably less than 0.25 crust.It does not consider the deposition problems of catalyzer in circulation line.
Find that produce in the method for acetate at the iridium catalyzed carbonylation, under some operational condition, catalysis system (being iridium catalyst and ruthenium promotor) may deposit and form solid.Usually, this solid is the composition of catalyzer and promotor, and usually for red or have a redness.Especially, when liquid reaction composition when second reaction zone, wherein at least 1% dissolving and/or the carbon monoxide carried secretly produce extra acetate at this reaction zone internal reaction, as describing among the EP-A-0846674.
Therefore, need a kind of improved carbonylation method, it can reduce in the acetic acid product removal process because of forming promotor and/or the catalyst loss that solid causes.
Have now found that, in acetate recovery stage and optional further reaction zone, can improve the stability of catalyst system and reduce loss by making carbon monoxide maintain the amount of determining.
Therefore, the invention provides a kind of method of producing acetate, the method comprising the steps of: (1) in first carbonylation reaction district, carbonylation methanol and/or its reactive derivatives in the liquid reaction composition that comprises iridium carbonylating catalyst, ruthenium promotor, methyl iodide promotor, methyl acetate, acetate and water; (2) take out liquid reaction composition by described carbonylation reaction district, and take out dissolving and/or the carbon monoxide of carrying secretly and other gas together; (3) the optional liquid reaction composition that makes described taking-up is by one or more further reaction zones, with the carbon monoxide that consumes at least a portion dissolving and/or carry secretly;
(4) make described composition enter one or more flash separation stages from step (2) and optional step (3), to form the gas fraction that (i) contains condensable components and low pressure exhaust gas, condensable components comprises acetic acid product, low pressure exhaust gas comprises carbon monoxide and dissolving and/or is entrained in other gas in the liquid carbonylation reaction composition of taking-up, (ii) liquid distillate comprises iridium carbonylating catalyst, ruthenium promotor and acetic acid solvent;
(5) from low pressure exhaust gas, isolate condensable components; And
(6) liquid distillate is circulated to the first carbonylation reaction district by flash separation stages,
Wherein keep the concentration of carbon monoxide in the low pressure exhaust gas according to following formula:
Y＞mX+C
Wherein Y is the volumetric molar concentration of carbon monoxide in the low pressure exhaust gas, and X is the concentration of ruthenium in the liquid reaction composition, by weight, represents with ppm, and m is about 0.012, and C is approximately-8.7.
The amount of method of the present invention by the carbon monoxide that will contact with promotor maintains on the level of qualification and solved above-mentioned technical problem.Found that this method can reduce because the loss that unstable caused of acetic acid product recovery stage promotor and/or catalyzer.
Though do not wish to be bound by any theory, but still think this precipitation be because, or to small part since ruthenium promotor in flash stage, form polymer form and cause.
Found because any sedimentary solid all can dissolve in turning back to carbonylation reactor the time again, sometimes still can tolerate unstable to a certain degree, if should instability surpass to a certain degree, then dissolution rate is less than sedimentation rate, and the ruthenium promotor in the reactor and the amount of iridium catalyst just descend.This just needs more promotors of adding and catalyzer to keep the activity of whole reactor.
Deposition solid itself also can produce operational problem, as the loss of material and the obstruction of technology and/or instrument lines.
First reaction zone can comprise traditional liquid-phase carbonylation reaction zone.The suitable pressure of carbonylation reaction is the 1-200 crust in first reaction zone, preferred 15-100 crust, more preferably 15-50 crust, and further preferred 18-35 crust.The optimal temperature of carbonylation reaction is 100-300 ℃ in first reaction zone, preferred 150-220 ℃.
Two reaction zones of preferred use, first and second reaction zones remain in the isolating reactor, employing is taken out in first reactor from the liquid reaction composition of first reactor and dissolving and/or the carbon monoxide carried secretly, it is sent into the mode of second reactor again.This isolating second reactor can comprise the pipeline part between first reactor and liquid reaction composition flash valve.Preferred this pipeline full of liquid.Usually length of pipeline diameter ratio can be about 12: 1, though bigger and littler slenderness ratio also can be used.
Usually, the carbon monoxide that takes out at least a portion liquid reaction composition and dissolving and/or carry secretly from first reactor, and the liquid that at least a portion is taken out and dissolving and/or the carbon monoxide carried secretly are sent into second reaction zone together.Preferably the response composite of all liquid basically that takes out from first reaction zone is admitted to second reaction zone with dissolving and/or the carbon monoxide carried secretly.
Second reaction zone can be operated under 100-300 ℃ temperature of reaction, preferred 150-230 ℃.Second reaction zone can be operated under the temperature that is higher than first reaction zone, exceeds usually to reach 20 ℃.Second reaction zone can be operated under the reaction pressure of 10-200 crust, preferred 15-100 crust.The pressure of preferred second reaction zone is equal to or less than the reaction pressure of first reaction zone.The suitable residence time of liquid reaction composition in second reaction zone is 5-300 second, preferred 10-100 second.
Except to the carbon monoxide that second reaction zone is introduced, also introducing carbon monoxide to second reaction zone as the carbon monoxide that dissolves and/or carry secretly.This additional carbon monoxide can combine with first liquid reaction composition before introducing second reaction zone altogether, and/or can add in second reaction zone separately to one or more positions.This additional carbon monoxide can contain impurity, for example H
2, N
2, CO
2And CH
4Additional carbon monoxide can be by forming from the high pressure exhaust gas of first reaction zone, and it can guarantee advantageously that first reaction zone operates under higher CO pressure, and carbon monoxide is sent in second reaction zone with higher flow velocity.In addition, also can save the needs of handle high voltages waste gas.
Additional carbon monoxide also can be made up of the air-flow that another kind contains carbon monoxide, for example from the logistics that is rich in carbon monoxide of another factory.
In the response composite that takes out by first reaction zone, preferably will be greater than 10%, more preferably greater than 25%, even more preferably greater than 50%, for example at least 95% dissolving and/or the carbon monoxide carried secretly consume in second reaction zone.
In the method for the present invention, suitable reactive derivatives of methanol comprises methyl acetate, dme and methyl iodide.Can use the composition of methyl alcohol and its reactive derivatives as reactant in the method for the present invention.For ether or ester reactant, also need water as co-reactant.Preferably, use methyl alcohol and/or methyl acetate as reactant.
By reacting with carboxylic acid product or solvent, at least some methyl alcohol and/or its reactive derivatives are converted into methyl acetate, and therefore are present in the liquid reaction composition as methyl acetate.Preferably, the concentration of the interior methyl acetate of liquid reaction composition is 1-70% weight independently in first and second reaction zones, and more preferably 2-50% weight most preferably is 3-35% weight.
Water can generate in liquid reaction composition on the spot, for example, generates by the esterification between methanol reactant and acetic acid product.Can separate with other component of liquid reaction composition or with other component, introduce water to the first and second carbonylation reaction districts independently.Water can be told from other component of the response composite of reaction zone taking-up, but and the water concentration of the water of recirculation limited amount needing in the liquid reaction composition to keep.Preferably, in first and second reaction zones in the liquid reaction composition water concentration be 0.1-20% weight independently, more preferably 1-15% weight, further 1-10% weight more preferably.
Preferably, the concentration of methyl iodide promotor independently is 1-20% weight in the interior liquid carbonylation reaction composition of first and second reaction zones, preferred 2-16% weight.
In first and second reaction zones in the liquid reaction composition, iridium catalyst can comprise dissolve in liquid reaction composition contain iridic compound arbitrarily.Can iridium catalyst be added in the liquid reaction composition any suitable form, it is dissolved in the liquid reaction composition maybe can be converted into the solution form.Preferred use not chloride iridic compound, acetate for example, it dissolves in one or more liquid reaction composition components, and for example therefore water and/or acetate can add in the reaction by its solution.The example that contains iridic compound in suitable the added to liquid reaction composition comprises IrCl
3, IrI
3, IrBr
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2, [Ir (CO)
2Br]
2, [Ir (CO)
4I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
2]
-H
+, [Ir (CH
3) I
3(CO)
2]
-H
+, Ir
4(CO)
12, IrCl
34H
2O, IrBr
34H
2O, Ir
3(CO)
12, iridium metals, Ir
2O
3, IrO
2, Ir (acac) (CO)
2, Ir (acac)
3, iridium acetate, [Ir
3O (OAc)
6(H
2O)
3] [OAc] and six chloro-iridic acid H
2[IrCl
6], preferred, not chloride iridium complex, for example acetate, oxalate and acetylacetate.
Preferably, in the liquid reaction composition of first and second reaction zones, iridium catalyst concentration independently is 100-6000ppm, in the weight of iridium.
In addition, liquid reaction composition also comprises at least a ruthenium promotor in first and second reaction zones.This promotor can comprise be dissolved in liquid reaction composition contain ruthenium compound arbitrarily.Can ruthenium promotor be added in the liquid reaction composition any suitable form, it is dissolved in the liquid reaction composition maybe can be converted into the solution form.Preferred use not chloride ruthenium promotor, acetate for example, it dissolves in one or more liquid reaction composition components, and for example therefore water and/or acetate can add in the reaction by its solution.
The spendable suitable example that contains ruthenium compound comprises ruthenium chloride (III), ruthenium chloride (III) trihydrate, ruthenium chloride (IV), ruthenium bromide (III), iodate ruthenium (III), ruthenium metal, ruthenium oxide, formic acid ruthenium (III), [Ru (CO)
3I
3]
-H
+, four (acetyl) ruthenium chloride (II, III), ruthenium acetate (III), propionic acid ruthenium (III), butyric acid ruthenium (III), pentacarbonyl ruthenium, ten dicarbapentaborane, three rutheniums, with blended halo carbonyl ruthenium, for example dichloro three ruthenium (II) dimer, dibromo three ruthenium (II) dimer and other organic ruthenium complex compound, two (4-cymene) two rutheniums (II) of tetrachloro, two (benzene) two rutheniums (II) of tetrachloro, dichloro (ring hot-1,5-diene) ruthenium (II) polymkeric substance and three (acetylacetonate) ruthenium (III) for example.
Preferably, it is free from foreign meter to contain ruthenium compound, and it provides or produce on the spot ion iodine, thereby but inhibited reaction, for example, alkali or alkaline-earth metal or other salt.
Preferred ruthenium promotor of using significant quantity, this significant quantity can be up to ruthenium promotor in liquid reaction composition and/or be recycled to solubility limit amount in the liquid process streams in carbonylation reaction district by the acetate recovery stage.The suitable mol ratio of ruthenium promotor in liquid reaction composition is every kind of ruthenium promotor: iridium is [0.1-100]: 1, preferred [greater than 0.5]: 1, more preferably [greater than 1]: 1, with preferred [the highest by 20]: 1, more preferably [the highest by 15]: 1, further more preferably [the highest by 10]: 1.
In each reaction zone of first and second reaction zones, the concentration of ruthenium promotor independently is less than 6000ppm in the liquid reaction composition.Suitable cocatalyst concentration is 400-5000ppm, as 2000-4000ppm.
Though preferably under the condition of not adding salt compounded of iodine (i.e. the salt of generation or disassociation iodide ion) basically, operate this method usually, also can tolerate this salt under certain conditions.Thereby, should be with the iodide ion impurity in the liquid reaction composition, as (a) corrosion metals, especially nickel, iron and chromium, (b) phosphine or nitrogenous compound or the part of quaternary saltization on the spot remain on minimum or remove, because the I that these materials produce in liquid reaction composition
-Speed of reaction is had disadvantageous effect, and it has negative impact to reaction usually.Found some corrosion metal contaminants, molybdenum for example is to I
-Generation more insensitive.By using suitable corrosion resistance structure material will have the corrosion metals of disadvantageous effect to reduce to minimum to speed of reaction.Equally, impurity is such as alkaline metal iodide, also should be controlled at minimum as the amount of lithium iodide.By using suitable ion exchange resin bed processing reaction composition or the logistics of preferably treatment catalyst recirculation, can reduce the amount of corrosion metals and other ionic impurity.US4 has described this technology in 007,130.Preferably, ionic impurity concentration is controlled at is lower than finite concentration, can only in liquid reaction composition, produce I under this concentration less than 500ppm
-, preferably less than the I of 250ppm
-, be more preferably less than the I of 50ppm
-
The reaction of carbon monoxide thing that is used for carbonylation reaction can be essentially pure, maybe can contain inert impurities, as carbonic acid gas, methane, nitrogen, rare gas element, water and C
1-C
4Paraffinic hydrocarbons.The hydrogen that preferably hydrogen in the carbon monoxide and steam is carried out conversion reaction and generate on the spot is controlled at lower level, for example less than the dividing potential drop of 1 crust, because the existence of hydrogen can cause forming hydrogenation products.The suitable independent 1-70 of being of carbon monoxide pressure of tension suitable in first and second reaction zones clings to preferred 1-35 crust, more preferably 1-15 crust.
Can use the flash separation method by the second reaction zone acetic acid product, and choose wantonly and reclaim, or reclaim respectively with first reactor with first reactor.In the flash separation, liquid reaction composition is passed through flash zone via flash valve.Flash stage can be the adiabatic flash device, maybe can have additional type of heating.In flash stage, but reactant, water and methyl iodide carbonylation catalyst promoters and the uncondensable gas of liquid distillate from containing the acetate carbonylation that contains most of iridium catalyst and most of ruthenium promotor separates as the steam cut of nitrogen, carbon monoxide, hydrogen and carbonic acid gas; Liquid distillate is circulated to first reaction zone, and the steam cut is admitted to one or more distillation zones.In first distillation zone, acetic acid product separates with light constituent (methyl iodide and methyl acetate).Light constituent is removed from cat head, and is recycled to first and/or second reaction zone.From the low pressure exhaust gas in addition that cat head is removed, it contains uncondensable gas, as nitrogen, carbon monoxide, hydrogen and carbonic acid gas.This lower-pressure exhaust flow is being put into air, for example by before the burning, can partly remove condensable materials by off gas treatment, as methyl iodide.
According to the present invention, the carbon monoxide concentration in the low pressure exhaust gas must be greater than the defined concentration of ruthenium concentration among formula Y＞mX+C.
Aptly, the carbon monoxide concentration in the low pressure exhaust gas is at least 30mol%, 30-60mol% for example, for example, and 30-40mol%, the ruthenium weight concentration in the liquid reaction composition can the highest 3000ppm.
Preferably, the carbon monoxide concentration in the low pressure exhaust gas is at least 50mol%, preferred 50-60mol%, and the ruthenium weight concentration in the liquid reaction composition can the highest 6000ppm.
More preferably, the carbon monoxide concentration in the low pressure exhaust gas is at least 55mol%, 55-65mol% for example, and the weight concentration of ruthenium can the highest 5500ppm in the liquid reaction composition.
The acetate of producing according to the inventive method can traditional method be further purified, and for example further impurity is removed in distillation, as water, unreacted carbonylation reactant and/or its ester derivative and high boiling point by-products produced.
Method of the present invention is preferably carried out in a continuous manner.
Only present invention is described by embodiment and with reference to the following example and Fig. 1 and Fig. 2 now.The schematic representation of apparatus of Fig. 1 for using among the embodiment.Fig. 2 is the influence to deposition of solids of carbon monoxide and ruthenium concentration.
Test A and embodiment/test 1-18
Equipment therefor as shown in Figure 1.With reference to figure 1, this device comprises the elementary carbonylation reactor (1) that band stirs, secondary carbonylation reactor (2), flash tank (3) and distillation tower (not shown).
Commercial grade methanol behind the scrubbing exhaust gas is carried out carbonylation reaction in 6 liters of primary reactor (1), be reflected under the existence of iridium carbonylating catalyst and ruthenium promotor to carry out, and pressure is 27.6 crust (2.76 * 10
6N/m
2), temperature is 190 ℃.Primary reactor (1) is equipped with agitator/water screw (4) and barrier (not shown), in order to guarantee the thorough mixing of liquids and gases reactant.Carbon monoxide is confessed by pressure bottle, and the jet apparatus (5) below being installed in agitator (4) enters primary reactor (1).In order to make the iron amount minimum that enters primary reactor (1), allow carbon monoxide pass through a carbon filter (not shown).Deep fat circulates by the chuck (not shown), thereby the reaction solution in the primary reactor (1) is remained under the constant temperature of reaction.For measuring the speed that solid forms, use the fouling rate on the near infrared ray transmitter that is positioned on the reactor sample loop to measure.Its service temperature is 90 ℃, is positioned at upwards logistics place that reactor outlet pipeline (flash line) is right after flash valve.Measure this incrustation with absorbance units/sky.
For removing rare gas element, from primary reactor (1), discharge high pressure exhaust gas through pipeline (6).High pressure exhaust gas makes it pass through the condenser (not shown) before valve (7) pressure release and before high pressure exhaust gas is fed to washing system.From primary reactor (1), take out liquid reaction composition along still well (8), in pipeline (9) enters the flash tank (3) that is under the reactor level control.In flash tank (3), liquid reaction composition is depressurized to 1.48 crust (1.48 * 10 through flash distillation
5N/m
2).Separating obtained gas and liquid composition; The liquid that is rich in catalyzer returns primary reactor (1) through pipeline (10) and pump (not shown), and steam directly enters the distillation tower (not shown) with the steam form afterwards by scum dredger (12).
The flash line (9) that is connected in the volume of secondary reactor (2) goes up and seperating vale is installed, thereby makes the fluid of discharging primary reactor (1) directly by flash valve or directly pass through secondary reactor (2) and pass through flash valve again.Secondary reactor (2) comprises the conduit of diameter 2.5cm, long 30cm, and it is about 4% or 8% of primary reactor (a 1) volume with the shared volume of the pipeline that is connected.Conduit is parallel to flash line (9) setting, and provides additional carbon monoxide through pipeline 14 conductive pipe.Secondary reactor (2) is identical with the working pressure of primary reactor (1).
Steam from scum dredger (12) enters the distillation tower (not shown), aqueous acetic acid is from the vapor recovery by distillation tower (not shown) side winding displacement (not shown) in distillation tower, and in the purification system (not shown), be further purified and dry, and the low pressure exhaust gas that contains carbon monoxide is delivered to the washer (not shown) before burning.
Test A
Use is according to the described apparatus and method of Fig. 1, the fluid of wherein discharging primary reactor (1) directly enters flash valve (that is to say and do not use secondary reactor), methyl alcohol is carbonylation in primary reactor (1), and temperature is 190 ℃, and stagnation pressure is 27.6 crust (2.76 * 10
6N/m
2).Take out liquid reaction composition from primary reactor (1) through pipeline (9).Liquid reaction composition in the primary reactor (1) contains the methyl iodide of 7% weight of having an appointment, the methyl acetate of about 10% weight, the water of about 4% weight, the acetate of about 79% weight, the iridium of 1450ppm and the ruthenium of 4450ppm.Liquid reaction composition from primary reactor (1) enters flash separator (3), and its working pressure is 1.48 crust (1.48 * 10
5N/m
2).Use above-mentioned near-infrared analysis method to measure fouling rate, the result is as shown in table 2.
Embodiment 1
Use is according to the described apparatus and method of Fig. 1, and methyl alcohol is carbonylation in primary reactor (1), and temperature is 190 ℃, and stagnation pressure is 27.6 crust (2.76 * 10
6N/m
2).Take out liquid reaction composition from primary reactor (1) through pipeline (9).Liquid reaction composition in the primary reactor (1) contains the methyl iodide of 7% weight of having an appointment, the methyl acetate of 11% weight, the water of 4% weight, the acetate of about 78% weight, the iridium of 1520ppm and the ruthenium of 4410ppm.Afterwards, the liquid reaction composition that will take out from primary reactor (1) changes secondary reactor (2) over to.Liquid reaction composition is further carbonylation in secondary reactor (2), and temperature is 190 ℃ of medium temperatures, and stagnation pressure is 27.6 crust (2.76 * 10
6N/m
2), the residence time is 40-50 second.
Liquid reaction composition from secondary reactor (2) enters flash separator (3), and working pressure is 1.48 crust (1.48 * 10
5N/m
2).Use above-mentioned near-infrared analysis method to measure fouling rate, the result is as shown in table 2.
Embodiment 2-4
Repeat the method for embodiment 1 according to the operational condition shown in the table 1.Carbon monoxide concentration in ruthenium concentration and the low pressure exhaust gas is as shown in table 2 to be changed.
Test 5-18
Except that ruthenium concentration greater than the carbon monoxide concentration in 6000ppm or the low pressure exhaust gas less than the 50mol%, adopt the method that repeats embodiment 1 according to other operational condition shown in the table 1.Carbon monoxide concentration in ruthenium concentration and the low pressure exhaust gas is as shown in table 2.
Table 1
| ?[H2O] ?wt％ | ?[MeI] ?wt％ | ?[MeOAc] ?wt％ | ?[Ir] ?ppm | ?[Ru] ?ppm | The second reactor CO charging g/h | The second reactor volume % | |
| Test A | ?4.4 | ?6.5 | ?9.6 | ?1450 | ?4450 | ?- | ?- |
| Embodiment 1 | ?4.3 | ?6.9 | ?11.2 | ?1460 | ?4330 | ?200 | ?8 |
| Embodiment 2 | ?4.1 | ?6.1 | ?7.7 | ?1460 | ?4300 | ?200 | ?8 |
| Embodiment 3 | ?4.2 | ?7.0 | ?10.1 | ?1440 | ?3370 | ?200 | ?8 |
| Embodiment 4 | ?4.1 | ?7.0 | ?10.6 | ?1530 | ?4920 | ?100 | ?4 |
| Test 5 | ?4.1 | ?7.3 | ?10.6 | ?1520 | ?4410 | ?- | ?8 |
| Test 6 | ?3.8 | ?6.2 | ?8.8 | ?1390 | ?4220 | ?130 | ?8 |
| Test 7 | ?4.5 | ?7.6 | ?10.6 | ?1400 | ?4270 | ?120 | ?8 |
| Test 8 | ?4.2 | ?6.7 | ?11.0 | ?1460 | ?3230 | ?140 | ?8 |
| Test 9 | ?4.2 | ?6.7 | ?10.4 | ?1460 | ?3220 | ?90 | ?8 |
| | ?4.4 | ?6.8 | ?10.6 | ?1450 | ?3210 | ?50 | ?8 |
| Test 11 | ?4.4 | ?6.8 | ?10.8 | ?1420 | ?2980 | ?10 | ?8 |
| Test 12 | ?4.4 | ?6.5 | ?10.1 | ?1490 | ?6210 | ?200 | ?8 |
| Test 13 | ?3.8 | ?6.5 | ?9.7 | ?1480 | ?6110 | ?150 | ?8 |
| Test 14 | ?3.9 | ?6.7 | ?10.5 | ?1420 | ?5750 | ?100 | ?8 |
| Test 15 | ?3.8 | ?6.5 | ?10.2 | ?1510 | ?4830 | ?10 | ?4 |
| Test 16 | ?5.1 | ?6.9 | ?12.6 | ?1830 | ?2430 | ?0 | ?8 |
| Test 17 | ?4.6 | ?7.5 | ?13.5 | ?1970 | ?2490 | ?0 | ?8 |
| Test 18 | ?4.6 | ?6.9 | ?9.7 | ?1550 | ?2880 | ?0 | ?8 |
Table 2 low pressure exhaust gas
| ?[Ru] ?ppm | Carbonylation rate mol/l/h | CO dividing potential drop (crust) | [CO] mol% in the low pressure exhaust gas | Fouling rate AU/ days | The second reactor outlet temperature ℃ | |
| Test A | ?4450 | ?22.0 | ?8.3 | ?48 | ?0.01 | ?- |
| Embodiment 1 | ?4430 | ?24.2 | ?7.8 | ?56 | ?0.01 | ?192.7 |
| Embodiment 2 | ?4300 | ?23.6 | ?9.5 | ?63 | ?0.01 | ?194.0 |
| Embodiment 3 | ?3370 | ?26.2 | ?11.5 | ?57 | ?0.01 | ?195.9 |
| Embodiment 4 | ?4920 | ?27.2 | ?11.8 | ?57 | ?0.00 | ?188.5 |
| Test 5 | ?4410 | ?25.2 | ?8.2 | ?32 | ?0.11 | |
| Test 6 | ?4220 | ?23.9 | ?8.2 | ?45 | ?0.11 | ?193.5 |
| Test 7 | ?4270 | ?28.9 | ?9.7 | ?45 | ?0.20 | ?195.4 |
| Test 8 | ?3230 | ?26.8 | ?11.2 | ?42 | ?0.06 | ?196.3 |
| Test 9 | ?3220 | ?24.9 | ?10.7 | ?31 | ?0.08 | ?195.7 |
| Test 10 | ?3210 | ?24.4 | ?10.2 | ?23 | ?0.06 | ?194.6 |
| Test 11 | ?2980 | ?23.5 | ?9.9 | ?13 | ?0.15 | ?193.0 |
| Test 12 | ?6210 | ?28.9 | ?9.8 | ?55 | ?0.02 | ?196.0 |
| Test 13 | ?6110 | ?30.1 | ?10.1 | ?47 | ?0.22 | ?196.2 |
| Test 14 | ?5750 | ?29.2 | ?10.3 | ?39 | ?0.42 | ?195.6 |
| Test 15 | ?4830 | ?27.4 | ?11.7 | ?42 | ?0.02 | ?189.3 |
| Test 16 | ?2430 | ?25.3 | ?9.7 | ?18 | ?0.05 | |
| Test 17 | ?2490 | ?24.6 | ?6.2 | ?7 | ?0.30 | |
| Test 18 | ?2880 | ?17.7 | ?8.1 | ?10 | ?0.08 |
From the result of embodiment 1-4 and test 5-18 as can be seen, the ruthenium promoter concentration is less than 6000ppm, and the carbon monoxide concentration in the low pressure exhaust gas is when being at least 50mol%, in fact deposition (incrustation) not.In addition, can find out also that the deposition degree meets the deposition that is produced when not having second reactor.When the carbon monoxide concentration in ruthenium promoter concentration and the low pressure exhaust gas exceeded this scope, deposition of solids speed (incrustation) clearly.
Embodiment 19-22, test 23
Repeat the method for embodiment 1 according to the operational condition shown in the table 3.Carbon monoxide concentration in ruthenium concentration and the low pressure exhaust gas is as shown in table 4 to be changed.
Table 3
| ?[H2O] ?wt％ | ?[MeI] ?wt％ | ?[MeOAc] ?wt％ | ?[Ir] ?ppm | ?[Ru] ?ppm | The second reactor CO charging g/h | The second reactor volume % | |
| Embodiment 19 | ?5.3 | ?7.0 | ?12.9 | ?1370 | ?4160 | ?- | ?- |
| | ?4.9 | ?6.2 | ?12.5 | ?1750 | ?3980 | ?0 | ?4 |
| Embodiment 21 | ?5.0 | ?6.9 | ?12.8 | ?1270 | ?3790 | ?0 | ?4 |
| Embodiment 22 | ?4.8 | ?6.7 | ?13.0 | ?1180 | ?3490 | ?- | ?- |
| Test 23 | ?5.0 | ?6.8 | ?12.6 | ?1750 | ?3850 | ?0 | ?4 |
Table 4
| ?[Ru] ?ppm | Carbonylation rate mol/l/h | CO dividing potential drop (crust) | [CO] mol% in the low pressure degree gas | Fouling rate AU/ days | |
| Embodiment 19 | ?4160 | ?20.2 | ?9.3 | ?60 | ?0.000 |
| | ?3980 | ?22.3 | ?9.4 | ?37 | ?-0.001 |
| Embodiment 21 | ?3790 | ?19.9 | ?9.9 | ?44 | ?0.003 |
| Embodiment 22 | ?3490 | ?18.8 | ?9.4 | ?59 | ?-0.001 |
| Test 23 | ?3850 | ?22.1 | ?9.0 | ?30 | ?-0.001 |
Embodiment 24-26 and test 27-34
Repeat the method for embodiment 1 according to the operational condition shown in the table 5.Carbon monoxide concentration in ruthenium concentration and the low pressure exhaust gas is as shown in table 6 to be changed.Determine fouling rate by placing on the strainer in the catalyst recycle line institute's cumulative solid.
Table 5
| ?[H2O] ?wt％ | ?[MeI] ?wt％ | ?[MeOAc] ?wt％ | ?[Ir] ?ppm | ?[Ru] ?ppm | The second reactor CO charging g/h | The second reactor volume % | |
| Embodiment 24 | ?4.9 | ?6.8 | ?12.1 | ?1530 | ?3440 | ?90 | ?8 |
| Embodiment 25 | ?4.7 | ?5.9 | ?12.2 | ?1390 | ?3220 | ?80 | ?8 |
| Embodiment 26 | ?5.2 | ?6.7 | ?11.7 | ?1580 | ?3370 | ?40 | ?8 |
| Test 27 | ?4.8 | ?7.2 | ?11.2 | ?1670 | ?3650 | ?60 | ?8 |
| Test 28 | ?5.0 | ?7.1 | ?11.9 | ?1570 | ?3380 | ?20 | ?8 |
| Test 29 | ?5.2 | ?6.6 | ?11.9 | ?1570 | ?3380 | ?0 | ?8 |
| | ?4.4 | ?6.5 | ?11.5 | ?1650 | ?4360 | ?60 | ?8 |
| Test 31 | ?4.9 | ?6.1 | ?11.8 | ?1680 | ?5130 | ?60 | ?8 |
| Test 32 | ?4.8 | ?6.7 | ?12.3 | ?1480 | ?4910 | ?60 | ?8 |
| Test 33 | ?5.0 | ?6.9 | ?11.8 | ?1410 | ?5780 | ?60 | ?8 |
| Test 34 | ?4.3 | ?6.2 | ?9.8 | ?1590 | ?6260 | ?60 | ?8 |
Table 6
| ?[Ru] ?ppm | Carbonylation rate mol/l/h | CO dividing potential drop (crust) | Low pressure exhaust gas [CO] mol% | Fouling rate g/h | |
| Embodiment 24 | ?3440 | ?22.1 | ?9.5 | ?57 | ?0.0038 |
| Embodiment 25 | ?3220 | ?21.3 | ?9.3 | ?52 | ?0.0034 |
| Embodiment 26 | ?3370 | ?21.0 | ?9.8 | ?35 | ?0.0037 |
| Test 27 | ?3650 | ?21.5 | ?9.3 | ?45 | ?0.0088 |
| Test 28 | ?3380 | ?20.9 | ?9.6 | ?27 | ?0.0043 |
| Test 29 | ?3380 | ?20.2 | ?9.9 | ?12 | ?0.0063 |
| | ?4360 | ?21.5 | ?9.2 | ?43 | ?0.0112 |
| Test 31 | ?5130 | ?22.6 | ?9.9 | ?42 | ?0.0123 |
| Test 32 | ?4910 | ?22.6 | ?8.2 | ?43 | ?0.0116 |
| Test 33 | ?5780 | ?21.9 | ?9.0 | ?40 | ?0.0090 |
| Test 34 | ?6260 | ?23.9 | ?9.9 | ?41 | ?0.0143 |
Can clearly find out that with the comparative result of test 27-34 keeping according to following formula of the carbon monoxide concentration in the low pressure exhaust gas carried out from table 6 embodiment 24-26:
Y＞mX+C
Wherein Y is the volumetric molar concentration of carbon monoxide in the low pressure exhaust gas, and X is the concentration of ruthenium in the liquid reaction composition, by weight, represents with ppm, and m is about 0.012, and C is approximately-8.7, and fouling rate significantly reduces.
The caption of Fig. 2 the relation between carbon monoxide concentration and ruthenium concentration and solid form in the low pressure exhaust gas.Data point among the figure is the result of embodiment and test among the above-mentioned table 1-6.Found a kind of relation (line that point is linked to be) from figure, its explanation keeps if the carbon monoxide concentration Y in the low pressure exhaust gas presses following formula, and then solid forms and reduces:
Y＞mX+C
Wherein Y is the volumetric molar concentration of carbon monoxide in the low pressure exhaust gas, and X is the concentration of ruthenium in the liquid reaction composition, by weight, represents with ppm, and m is about 0.012, and C is approximately-8.7.Fouling rate was greater than 0.01AU/ days or 0.004g/h place, and can think has solid to form.
Claims (30)
1. method of producing acetate, the method comprising the steps of:
(1) in first carbonylation reaction district, carbonylation methanol and/or its reactive derivatives in the liquid reaction composition that comprises iridium carbonylating catalyst, ruthenium promotor, methyl iodide promotor, methyl acetate, acetate and water;
(2) take out liquid reaction composition together with dissolving and/or the carbon monoxide of carrying secretly and other gas by described carbonylation reaction district;
(3) the optional liquid reaction composition that makes described taking-up is by one or more further reaction zones, with the carbon monoxide that consumes at least a portion dissolving and/or carry secretly;
(4) make described composition enter one or more flash separation stages from step (2) and optional step (3), to form the vapor fraction that (i) contains condensable components and low pressure exhaust gas, condensable components comprises acetic acid product, comprise carbon monoxide and dissolving with low pressure exhaust gas and/or be entrained in other gas in the liquid carbonylation reaction composition of taking-up, (ii) liquid distillate comprises iridium carbonylating catalyst, ruthenium promotor and acetic acid solvent;
(5) from low pressure exhaust gas, isolate condensable components; And
(6) liquid distillate is recycled to the first carbonylation reaction district by flash separation stages,
Wherein keep the concentration of carbon monoxide in the low pressure exhaust gas according to following formula:
Y＞mX+C
Wherein Y is the volumetric molar concentration of carbon monoxide in the low pressure exhaust gas, and X is the concentration of ruthenium in the liquid reaction composition, by weight, represents with ppm, and m is about 0.012, and C is approximately-8.7.
According to the process of claim 1 wherein the liquid reaction composition of taking out from first reaction zone together with dissolving and/or the carbon monoxide carried secretly by second reaction zone.
3. according to the method for claim 2, wherein whole basically liquid reaction composition of taking out from first reaction zone and dissolving and/or the carbon monoxide carried secretly are sent into second reaction zone together.
4. according to each method among the claim 1-3, wherein except to the carbon monoxide that second reaction zone is introduced, also introducing carbon monoxide to second reaction zone as dissolving and/or the carbon monoxide carried secretly.
5. according to the method for claim 4, wherein additional carbon monoxide can combine with first liquid reaction composition before introducing second reaction zone altogether, and/or can add the one or more positions in second reaction zone separately.
6. according to the method for claim 4 or 5, wherein additional carbon monoxide contains impurity.
7. according to each method among the claim 4-6, wherein additional carbon monoxide contains the high pressure exhaust gas from first reaction zone.
8. according to each method among the claim 4-6, wherein additional carbon monoxide contains the air-flow of carbon monoxide.
9. according to each method among the claim 1-8, wherein in the liquid reaction composition of being taken out by first reaction zone, dissolving greater than 10% and/or the carbon monoxide of carrying secretly consume in second reaction zone.
10. according to each method among the claim 1-8, wherein in the liquid reaction composition of being taken out by first reaction zone, dissolving greater than 25% and/or the carbon monoxide of carrying secretly consume in second reaction zone.
11. according to each method among the claim 1-8, wherein in the liquid reaction composition of being taken out by first reaction zone, dissolving greater than 50% and/or the carbon monoxide of carrying secretly consume in second reaction zone.
12. according to each method among the claim 1-11, wherein in first reaction zone with carbon monoxide carbonylation methanol and/or methyl acetate.
13. according to each method among the claim 1-12, wherein in first and second reaction zones in the liquid reaction composition concentration of methyl acetate independently be 1-70% weight.
14. according to each method among the claim 1-13, wherein in first and second reaction zones in the liquid reaction composition water concentration independently be 0.1-20% weight.
15. according to each method among the claim 1-14, wherein in first and second reaction zones in the liquid reaction composition concentration of methyl iodide promotor independently be 1-20% weight.
16. according to each method among the claim 1-15, wherein in the liquid reaction composition of first and second reaction zones, iridium carbonylating catalyst concentration independently is 100-6000ppm.
17. according to each method among the claim 1-16, wherein in the liquid reaction composition of first and second reaction zones, the content of ruthenium promotor is every kind of ruthenium promotor: the mol ratio of iridium is [0.1-100]: 1.
18. according to each method among the claim 1-17, wherein in the liquid reaction composition of first and second reaction zones, the content of ruthenium promotor is every kind of ruthenium promotor: the mol ratio of iridium is [the highest by 10]: 1.
19. according to each method among the claim 1-18, wherein in the liquid reaction composition of first and second reaction zones, ruthenium concentration independently is less than 6000ppm.
20. according to each method among the claim 1-19, wherein in the liquid reaction composition of first and second reaction zones, ruthenium concentration independently is 400-5000ppm.
21. according to each method among the claim 1-20, wherein in first and second reaction zones, carbon monoxide pressure of tension independently is the 1-70 crust.
22. according to each method among the claim 1-21, wherein in first and second reaction zones, carbon monoxide pressure of tension independently is the 1-15 crust.
23. according to each method among the claim 1-22, wherein the carbon monoxide concentration in the low pressure exhaust gas is 30mol% at least, the highest 3000ppm weight of ruthenium concentration in the liquid reaction composition.
24. according to claim 23 method, wherein the carbon monoxide concentration in the low pressure exhaust gas is 30-40mol%, the highest 3000ppm weight of ruthenium concentration in the liquid reaction composition.
25. according to each method among the claim 1-22, wherein the carbon monoxide concentration in the low pressure exhaust gas is 50mol% at least, the highest 6000ppm weight of ruthenium concentration in the liquid reaction composition.
26. according to the method for claim 25, wherein the carbon monoxide concentration in the low pressure exhaust gas is 50-60mol%, the highest 6000ppm weight of ruthenium concentration in the liquid reaction composition.
27. according to each method among the claim 1-22, wherein the carbon monoxide concentration in the low pressure exhaust gas is 55mol% at least, the highest 5500ppm weight of ruthenium concentration in the liquid reaction composition.
28. according to the method for claim 27, wherein the carbon monoxide concentration in the low pressure exhaust gas is 55-65mol.%, the highest 5500ppm weight of ruthenium concentration in the liquid reaction composition.
29. according to each method among the claim 1-28, wherein this method is carried out in a continuous manner.
30. the purposes of the carbon monoxide in the low pressure exhaust gas, in the production process of acetate, this carbon monoxide keeps the concentration according to following formula in low pressure exhaust gas:
Y＞mX+C
Wherein Y is the volumetric molar concentration of carbon monoxide in the low pressure exhaust gas, X is the concentration of ruthenium in the liquid reaction composition, by weight, represent with ppm, m is about 0.012, and C is approximately-8.7, and this production method comprises step: (1) in first carbonylation reaction district, carbonylation methanol and/or its reactive derivatives in the liquid reaction composition that comprises iridium carbonylating catalyst, ruthenium promotor, methyl iodide promotor, methyl acetate, acetate and water;
(2) take out liquid reaction composition and dissolving and/or the carbon monoxide of carrying secretly and other gas by described carbonylation reaction district;
(3) the optional liquid reaction composition that makes described taking-up is by one or more further reaction zones, with the carbon monoxide that consumes at least a portion dissolving and/or carry secretly;
(4) make described composition enter one or more flash separation stages from step (2) and optional step (3), to form the vapor fraction that (i) contains condensable components and low pressure exhaust gas, condensable components comprises acetic acid product, comprise carbon monoxide and dissolving with low pressure exhaust gas and/or be entrained in other gas in the liquid carbonylation reaction composition of taking-up, (ii) liquid distillate, it comprises iridium carbonylating catalyst, ruthenium promotor and acetic acid solvent;
(5) from low pressure exhaust gas, isolate condensable components; And
(6) liquid distillate is recycled to the first carbonylation reaction district by flash separation stages,
Loss with catalyzer and/or promotor in the minimizing acetic acid product removal process.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0211560.8 | 2002-05-20 | ||
| GBGB0211560.8A GB0211560D0 (en) | 2002-05-20 | 2002-05-20 | Process |
| PCT/GB2003/001592 WO2003097567A1 (en) | 2002-05-20 | 2003-04-09 | Process for the production of acetic acid |
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| US (1) | US7202382B2 (en) |
| EP (1) | EP1506151B1 (en) |
| JP (2) | JP4575149B2 (en) |
| KR (1) | KR100969842B1 (en) |
| CN (1) | CN1656053B (en) |
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| AU (1) | AU2003233860A1 (en) |
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| RS (1) | RS51825B (en) |
| RU (1) | RU2320638C2 (en) |
| TW (1) | TWI339202B (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097319A (en) * | 2017-12-19 | 2018-06-01 | 宁夏大学 | Carbonylation prepares rhodium ruthenium combination bimetallic catalyst of acetic acid and preparation method thereof |
| CN110937989A (en) * | 2018-09-21 | 2020-03-31 | 中国石油化工股份有限公司 | Synthesis method of acetic acid |
| TWI744336B (en) * | 2016-06-14 | 2021-11-01 | 英商億諾斯乙醯基英國有限公司 | Process |
| CN114828977A (en) * | 2019-12-17 | 2022-07-29 | 英力士乙酰英国有限公司 | Separation method and apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB0601865D0 (en) | 2006-01-30 | 2006-03-08 | Bp Chem Int Ltd | Process |
| GB0601861D0 (en) * | 2006-01-30 | 2006-03-08 | Bp Chem Int Ltd | Process |
| TWI465424B (en) * | 2006-03-21 | 2014-12-21 | Bp Chem Int Ltd | Process for the production of acetic acid |
| EP2093209A1 (en) * | 2008-02-19 | 2009-08-26 | BP Chemicals Limited | Process for the production of acetic acid |
| US8168822B2 (en) * | 2009-07-07 | 2012-05-01 | Celanese International Corporation | Acetic acid production by way of carbonylation with enhanced reaction and flashing |
| DE102010040921A1 (en) | 2010-09-16 | 2012-03-22 | Basf Se | Process for the preparation of acrylic acid from methanol and acetic acid |
| US8530696B2 (en) | 2010-09-24 | 2013-09-10 | Celanese International Corporation | Pump around reactor for production of acetic acid |
| US8877963B2 (en) * | 2010-09-28 | 2014-11-04 | Celanese International Corporation | Production of acetic acid with high conversion rate |
| US8394988B2 (en) | 2010-09-28 | 2013-03-12 | Celanese International Corporation | Production of acetic acid with high conversion rate |
| SG191374A1 (en) | 2010-12-30 | 2013-08-30 | Celanese Int Corp | Purification of acetic acid product streams |
| US9663437B2 (en) * | 2011-09-13 | 2017-05-30 | Celanese International Corporation | Production of acetic acid with high conversion rate |
| US20140121403A1 (en) | 2012-10-31 | 2014-05-01 | Celanese International Corporation | Integrated Process for the Production of Acrylic Acids and Acrylates |
| US9120743B2 (en) | 2013-06-27 | 2015-09-01 | Celanese International Corporation | Integrated process for the production of acrylic acids and acrylates |
| GB202005016D0 (en) * | 2020-04-06 | 2020-05-20 | Bp Chem Int Ltd | Process for producing acetic acid |
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| US5237097A (en) * | 1990-02-09 | 1993-08-17 | Quantum Chemical Corporation | Catalytic carbonylation process |
| US5672743A (en) * | 1993-09-10 | 1997-09-30 | Bp Chemicals Limited | Process for the production of acetic acid |
| FR2726556B1 (en) * | 1994-11-04 | 1996-12-20 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF CARBOXYLIC ACIDS BY CARBONYLATION IN THE PRESENCE OF IRIDIUM |
| US5510524A (en) * | 1995-02-21 | 1996-04-23 | Bp Chemicals Limited | Process for the production of a carboxylic acid |
| GB9625335D0 (en) * | 1996-12-05 | 1997-01-22 | Bp Chem Int Ltd | Process |
| GB9626324D0 (en) * | 1996-12-19 | 1997-02-05 | Bp Chem Int Ltd | Process |
| GB9626429D0 (en) * | 1996-12-19 | 1997-02-05 | Bp Chem Int Ltd | Process |
| FR2795410B1 (en) | 1999-06-22 | 2002-12-27 | Acetex Chimie | PROCESS FOR IMPROVING THE STABILITY AND / OR AVOIDING THE DEACTIVATION OF THE CATALYST DURING THE MANUFACTURE OF ACETIC ACID AND / OR METHYL ACETATE |
| GB9926854D0 (en) * | 1999-11-12 | 2000-01-12 | Bp Chem Int Ltd | Process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI744336B (en) * | 2016-06-14 | 2021-11-01 | 英商億諾斯乙醯基英國有限公司 | Process |
| CN108097319A (en) * | 2017-12-19 | 2018-06-01 | 宁夏大学 | Carbonylation prepares rhodium ruthenium combination bimetallic catalyst of acetic acid and preparation method thereof |
| CN110937989A (en) * | 2018-09-21 | 2020-03-31 | 中国石油化工股份有限公司 | Synthesis method of acetic acid |
| CN110937989B (en) * | 2018-09-21 | 2022-09-20 | 中国石油化工股份有限公司 | Synthesis method of acetic acid |
| CN114828977A (en) * | 2019-12-17 | 2022-07-29 | 英力士乙酰英国有限公司 | Separation method and apparatus |
| CN114828977B (en) * | 2019-12-17 | 2024-05-07 | 英力士乙酰英国有限公司 | Separation method and apparatus |
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| ES2344733T3 (en) | 2010-09-06 |
| KR100969842B1 (en) | 2010-07-13 |
| RU2320638C2 (en) | 2008-03-27 |
| GB0211560D0 (en) | 2002-06-26 |
| US20050165251A1 (en) | 2005-07-28 |
| RS99604A (en) | 2007-02-05 |
| EP1506151A1 (en) | 2005-02-16 |
| JP4575149B2 (en) | 2010-11-04 |
| CA2482794A1 (en) | 2003-11-27 |
| DE60332936D1 (en) | 2010-07-22 |
| TW200307048A (en) | 2003-12-01 |
| EP1506151B1 (en) | 2010-06-09 |
| JP2010265275A (en) | 2010-11-25 |
| CN1656053B (en) | 2010-05-05 |
| AU2003233860A1 (en) | 2003-12-02 |
| ATE470653T1 (en) | 2010-06-15 |
| RU2004137483A (en) | 2005-10-20 |
| US7202382B2 (en) | 2007-04-10 |
| RS51825B (en) | 2012-02-29 |
| KR20040111557A (en) | 2004-12-31 |
| TWI339202B (en) | 2011-03-21 |
| JP2005526131A (en) | 2005-09-02 |
| MY139536A (en) | 2009-10-30 |
| CA2482794C (en) | 2011-06-07 |
| WO2003097567A1 (en) | 2003-11-27 |
| UA79287C2 (en) | 2007-06-11 |
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Effective date of registration: 20210916 Address after: England Hampshire Patentee after: Ineos acetyl UK Ltd. Address before: The Middlesex County Patentee before: BP Chemicals Ltd. |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20100505 |